Vettel won his fourth pole of the Formula One season with a qualifying lap of 1 minute, 23.755 seconds, on the winding 3.6-mile course at Monza, followed by Webber with a time of 1:23.968.
"The car has been fantastic so far this weekend," Vettel said. "It was better than what we had expected. We had a really strong pace (in Friday's practice), and we were able to take that into qualifying."
Vettel and Webber were enthusiastic about their prospects Sunday on a track where Red Bull has not performed particularly well. Red Bull has just one top-three finish in 16 races at Monza, where 10 of the past 13 Italian Grand Prix winners started on the pole.
Pirelli reported its tires performed as expected in the warm, dry conditions.
Most drivers started out with the quicker hard-rubber tires and switched to slower softer medium tires later in the day.
"[Sunday] we are expecting to see most of the teams adopting a one-stop strategy, with the uncertainty being whether they will choose to start on the medium or hard compounds," Pirelli motorsports director Paul Hembrey said in a statement. "Even though we're expecting slightly cooler weather for the race there will still be huge demands on the tires, but so far blistering has not been an issue."